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We present a multi-reference configuration mixing scheme for describing ground and excited states, with well defined spin and space group symmetry quantum numbers, of the one-dimensional Hubbard model with nearest-neighbor hopping and…

Strongly Correlated Electrons · Physics 2013-06-28 R. Rodríguez-Guzmán , Carlos A. Jiménez-Hoyos , R. Schutski , Gustavo E. Scuseria

Excited-state gradients and derivative couplings are critical for simulating excited-state dynamics. However, their calculations are very expensive within the coupled-cluster framework due to the steep scaling. In this work, we present two…

Chemical Physics · Physics 2025-09-09 Chongxiao Zhao , Chenyang Li , Wenjie Dou

The present paper introduces a new multi-reference perturbation approach developed at second order, based on a Jeziorsky-Mokhorst expansion using individual Slater determinants as perturbers. Thanks to this choice of perturbers, an…

Chemical Physics · Physics 2017-06-28 Emmanuel Giner , Celestino Angeli , Yann Garniron , Anthony Scemama , Jean-Paul Malrieu

The exploration of the root structure of coupled cluster equations holds both foundational and practical significance for computational quantum chemistry. This study provides insight into the intricate root structures of these non-linear…

Chemical Physics · Physics 2024-09-12 Svala Sverrisdóttir , Fabian M. Faulstich

Methods able to simultaneously account for both static and dynamic electron correlations have often been employed, not only to model photochemical events, but also to provide reference values for vertical transition energies, hence allowing…

Chemical Physics · Physics 2022-04-26 Rudraditya Sarkar , Pierre-François Loos , Martial Boggio-Pasqua , Denis Jacquemin

In this article we report a stochastic evaluation of the recently proposed LCC multireference perturbation theory [Sharma S., and Alavi A., J. Chem. Phys. 143, 102815, (2015)]. In this method both the zeroth order and first order…

Chemical Physics · Physics 2017-03-08 Guillaume Jeanmairet , Sandeep Sharma , Ali Alavi

Molecules that have been suggested to violate the Hund's rule, having a first excited singlet state (S$_1$) energetically below the triplet state (T$_1$), are rare. Yet, they hold the promise to be efficient light emitters. Their…

Chemical Physics · Physics 2025-09-23 Atreyee Majumdar , Raghunathan Ramakrishnan

This study explores the electronic structure of the CH$_2$ molecule, modeled as a (6e, 23o) system using a 52-qubit quantum experiment, which is relevant for interstellar and combustion chemistry. We focused on calculating the dissociation…

The recent development of the density matrix renormalization group (DMRG) method in multireference quantum chemistry makes it practical to evaluate static correlation in a large active space, while dynamic correlation provides a critical…

Strongly Correlated Electrons · Physics 2020-08-20 Zhen Luo , Yingjin Ma , Xicun Wang , Haibo Ma

The excited state energy spectrum of a two-dimensional dimer system SrCu$_2$(BO$_3$)$_2$ has been investigated by high field ESR. Various types of multiple-triplet bound states-excited singlet, triplet and quintet states are identified,…

Strongly Correlated Electrons · Physics 2009-11-07 H. Nojiri , H. Kageyama , Y. Ueda , M. Motokawa

In the framework of the computational determination of highly-accurate vertical excitation energies in small organic compounds, we explore the possibilities offered by the equation-of-motion formalism relying on the approximate fourth-order…

This chapter presents the theory behind the CASPT2 method and its adaptation to a multi-state formalism. The chapter starts with an introduction of the theory of the CASPT2 method - an application of Rayleigh-Schr\"odinger perturbation…

Chemical Physics · Physics 2023-05-12 Stefano Battaglia , Ignacio Fdez. Galván , Roland Lindh

Hierarchy configuration interaction (hCI) has been recently introduced as an alternative configuration interaction (CI) route combining excitation degree and seniority number, which showed to efficiently recover both dynamic and static…

Chemical Physics · Physics 2024-02-20 Fábris Kossoski , Pierre-François Loos

Rydberg excited states of molecules pose a challenge for electronic structure calculations because of their highly diffuse electron distribution. Even large and elaborate atomic basis sets tend to underrepresent the long-range tail, overly…

We present a novel and cost-effective approach of using a second similarity transformation of the Hamiltonian to include the missing higher-order terms in the second-order approximate coupled cluster singles and doubles (CC2) model. The…

Chemical Physics · Physics 2022-01-26 Soumi Haldar , Achintya Kumar Dutta

We extend first-order multiconfigurational symmetry-adapted perturbation theory, SAPT(MC), [Hapka M. et al. JCTC, 2021, 17], to account for double-exchange effects, where up to two electron pairs are exchanged between interacting monomers.…

Chemical Physics · Physics 2025-04-21 Dominik Cieśliński , Michał Przybytek , Grzegorz Chałasiński , Michał Hapka

We present relativistic many-body perturbation theory plus configuration interaction (MBPT+CI) calculations of the lowest four excited states of Ni$^{12+}$, a promising candidate for highly charged ion (HCI) optical clocks. By combining the…

Atomic Physics · Physics 2026-01-01 Shi-cheng Yu , Hua Guan , Lei She , Cheng-Bin Li

The interaction between excited states of a closed-shell chromophore and a nearby free radical species gives rise to spin-coupled doublet states, namely singdoublet and tripdoublet, as well as a quartet state. This coupling facilitates…

Chemical Physics · Physics 2025-03-25 Chenyu Liu , Yang Xu , Peng Bao , Yangyi Lu , Jiali Gao

Ab initio methods based on the second-order and higher connected moments, or cumulants, of a reference function have seen limited use in the determination of correlation energies of chemical systems throughout the years. Moment-based…

Chemical Physics · Physics 2023-08-25 Brad Ganoe , Martin Head-Gordon

We introduce a perturbative approximation to the combined density functional theory and multireference configuration interaction (DFT/MRCI) method. The method, termed DFT/MRCI(2), results from the application of quasi-degenerate…

Chemical Physics · Physics 2022-11-09 Simon P. Neville , Michael S. Schuurman